Flame retardants for blends of natural and synthetic fibers

ABSTRACT

A process for rendering synthetic materials, of synthetic fibers or mixtures of the same flame resistant which entails employing water insoluble flame retardant agents which are treated as colorless pigments, reduced to extremely finely divided condition, suspended in latex medium and applied as such or as part of a dispersed dye paste to the fabric, dried and set in place. The active flame retardant agents are brominated organic chemical compounds, and reduced to a fine state of subdivision, preferably under two microns, average particle diameter, which compound is supported in an aqueous suspension with a colloidal protective agent, and thus, is in a form for blending in a binder, plastic resin latex, so that when the composition is dried and cured in place on the fabric, a very useful retardant effect is obtained which is durable to laundering and dry cleaning, and the hand of the fabric is preserved.

United States Patent [191 Mischutin [451 Apr. 15, 1975 FLAME RETARDANTSFOR BLENDS OF NATURAL AND SYNTHETIC FIBERS 75 Inventor; VladimirMischutin, Union City,

[73] Assignee: White Chemical Corporation,

Bayonne, NJ.

[22] Filed: Oct. 25, 1972 21 Appl. No.: 330,731

[52] US. Cl. 428/290; 252/81; 427/290; 427/428; 427/358; 428/921 [51]Int. Cl. C09k 3/28; C09d 5/18 [58] Field of Search 117/137, 136,111F,l21; 106/15 FP; 252/81 [56] References Cited UNITED STATES PATENTS2,668,294 2/1954 Gilpin 117/155 UA 2,912,392 11/1959 Stilbert et al.117/137 X 3,047,425 7/1962 Hirshfeld et a1. 117/136 X 3,093,599 6/1963Mueller-Tamm et al. 117/136 UX 3,658,634 4/1972 Yanagi 106/15 FP3,668,155 6/1972 Raley 252/8.1 X 3,715,310 2/1973 Butcher 252/8.l3,770,577 11/1973 Humphrey 117/137 X FOREIGN PATENTS OR APPLICATIONS1,191,569 3/1968 Germany 117/136 Primary Examiner-Harry .l. GwinnellAttorney, Agent, or Firm-Thomas B. Graham [57] ABSTRACT A process forrendering synthetic materials, of synthetic fibers or mixtures of thesame flame resistant which entails employing water insoluble flameretardant agents which are treated as colorless pigments, reduced toextremely finely divided condition, suspended in latex medium andapplied as such or as part of a dispersed dye paste to the fabric, driedand set in place.

9 Claims, No Drawings FLAME RETARDANTS FOR BLENDS OF NATURAL ANDSYNTHETIC FIBERS RELATED APPLICATION This application is related to mycopending application, Ser. No. 300,732, filed of even date herewith,incorporated herein fully.

BACKGROUND OF THE INVENTION Purely for safety purposes, flame retardanceor flame resistance of a fabric is a highly desirable characteristic. Ofmany methods available for developing various levels of flame retardancyall possess a variety of disadvantages, the principal ones being theinability of the flame retardant material, or treatment, to last throughlaundering or dry cleaning operations. Another principal disadvantage oftreatments of fabrics to develop this characteristic of flame retardanceis the loss of hand in the substrate. The problem is greatly aggravatedin some areas of handling, particularly where it is necessary to meetstatutory requirements for flame retardance in garments. Their physicalcondition being in the form of a bundle of fine fibers invites andencourages the sustenance of a flame if one gets started in the fabric.That is, a large area of oxidation is presented to any flame which getsstarted.

It is accordingly a basic object of this invention to provide a methodemploying familiar techniques in the textile industry for theapplication of flame retardant materials to textile fibers, whether thefibers be in the form of woven cloth, knitted cloth or in the form ofballs of the thread prior to being woven into cloth.

Other objects and advantages of the invention will be in part be obviousand in part appear hereinafter.

DESCRIPTION OF THE INVENTION Flame retardants for textiles and relatedmaterials of the durable type have been found to possess a multitude ofside effects which would either render the flame retarded substrateunusuable or reduce its useful life. In addition, most commonly usedmethods will be effective on one particular substrate while completelyineffective on others or blends of the same.

The present invention relates to a new method of flame retarding textileand related materials using a commonly employed method in pigmentprinting and dyeng, that is, through the use of a primary binder whichserves as an adhesive to fasten the flame retardant to a givensubstrate. In addition this technique can also be employed to flameretard the said binders, which normally are emulsions of syntheticpolymeric materials which are highly flammable and contribute to theflammability of flame retarded substrates.

The subject of the present invention consists of two basic elements, theflame retardant element and a binding element.

The flame retarding element is a colorless highly halobrominated,organic compound, solid at room temperature, possessing high melting anddecomposition points, which is easily reduced to an extremely smallparticle size by conventional means of grinding. The solid flameretardant material is reduced to a submicron or micron particle size andsuspended in water in a fashion similar to the preparation of pigmentdisper sions. In some cases, especially when extremely heat stablematerials are used, a synergist which will contribute to render thehalobrominated solids more heat unstable must be-employed. Thissynergist must possess similar characteristics to the halobrominatedflame retardant, that is, it is a micropulverized solid possessing goodheat stability, finely dispersed in water. In addition it must reactwith the halobrominated flame retarder at combustion temperatures toform a gaseous non-flammable gas which will prevent oxygen from reachingthe flaming substrate, thus impeding the oxidation process.

The second element used in this invention is an emulsion of a highmolecular weight polymer, commonly referred to as latex. The polymeremployed can be the result of polymerizing acrylic acid, methacrylicacid, acrylamide, methacrylamide, acrylonitrile, esters of acrylic andmethacrylicacids, vinyl chloride, vinylidene chloride, styrene,butadiene, maleic or fumaric acids and esters of same and the like. Thepolymer can be homopolymers or copolymers of the above describedmonomers. These emulsion polymers are commercially available indiffering grades depending on the ultimate properties desired. They havein common the fact that they form films at room or elevatedtemperatures, alone or in the presence of plasticizers. The propertiesof the film depend on the chemical composition of the same.

Due to the fact that the latexes possess extremely good adhesiveproperties, they are normally used for bonding purposes. They are usedfor bonding of pigments to hard to dye substrates, to bond fibers withfibers to obtain non woven fabrics, to bond fibers to fabrics to produceflocked fabrics and to bond fabrics to fabrics, fabrics to foams,fabrics to films, to non wovens, etc., to obtain laminated fabrics. Theyare also used for fabric backcoating to achieve various effects such asdimensional stability, to prevent ravelling, to give fabricsnon-slipping characteristics, with a filler, to impart opacity to thesame, etc., and for finishing to achieve dimensional stability, toincrease strength, decreasae air permeability, impart waste repellency,etc.

This invention relates to two uses of these materials:

a. To bond the flame retardant to non-reactive substrates by the use oflatex adhesives; and

b. To use the flame retardant to make the latex films non-combustible orself extinguishing when they are applied to flame retarded substrates.

In this application the solid flame retardant is the predominantingredient and the latex is the minor ingredient.

The micropulverized solid flame retardant is first dispersed in watercontaining a wetting agent by adding it slowly to the aqueous phaseunder strong agitation, with a high speed, high shear mixer. Afteraddition of the solid has been completed, the resulting dispersion isstabilized by adding small quantities of a protective colloid (commonlycalled thickener) such as carboxy methyl cellulose, methoxy orethoxycellulose of selected molecular weight to achieve an optimumviscosity and prevent the particles from settling.

The FR (flame retardant) is now diluted with water to a predeterminedstrength and sufficient amount of latex to achieve adhesion is added.This solution is now applied to the substrate by dipping it into thissolution and removing the excess by squeezing between two rollers. Thew'et substrate is now air dried at any convenient temperature and bakedat C. to C. for to 90 seconds.

The resulting material is flame retardant when tested by commonly usedflammabililty tests and the flame retardant is not lost after multiplelaunderings and/or dry cleanings. The feel or hand of the flame retardedmaterial is unchanged, but can be made stiff, if desirable, by selectinga harder latex.

The FR dispersion prepared as described above, is diluted in water, thelatex is added and the viscosity adjusted by the use of a thickener.

This treating batch is now applied by different techniques depending onthe final effect desired. It can be padded, knife coated, roller coated,sprayed, roller printed, screen printed, applied by saturation and thelike. The substrates are now air dried at any convenient temperature,and baked as above.

This technique is usually employed when the substrate to which the latexis applied is either intrinsically flame retardant or has been flameproofed in a separate operation. It can be used to flame retard latices,which will be employed as flocking adhesives, for fabric backcoating,pigment dyeing or printing, bonding or non woven fabric lamination andthe like.

The process of this invention is applicable to textile materials, instaple, tow, yarn, fiber, woven fabrics, non-woven fabrics, circular andflat knits, carpets and the like, to paper, to films, to foams, etc.

The substrate can be of natural origin such as cotton, linen, jute, cocofiber, wool, silk and the like, man made such as regenerated cellulose,cellulose diand triacetates, fiberglass and the like or syntheticpolymeric materials such as nylon, polyester, acrylics, polypropyleneand the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention utilizesbrominated aromatic compounds, preferably brominated as flame retardingmaterials. The preferred aromatic compounds employed are derivatives ofBenzene Where A through N are the same can be H, Br, CH C I'I Ca 7,

. or different and CH and the like; and X, Y, Z can be the same ordifferent and can be H, CH C H C 1, s s

Bis (hexachlorocyclopentadieno)-cycl00ctane 01 V BlDibromohexachloroeyclopentadienocyclooctaue N lN -ethylbis(dibromonorbornene) -dicarb0xamide The preferred entities are: 1.Polybrominated benzenes of the general formula:

I E I where A to F are the same or different and may be H, Br, with atleast one Br present on the benzene ring.

2. Polybromo monoalkyl benzene of the general formula:

where R may be alkyl, preferably of 1-5 carbons such as methyl, ethyl,propyl, butyl, pentyl, isopropyl, tertbutyl; unsaturated alkyls,haloalkyl or polyhaloalkyl wherein the moiety may include up to fourbromine atoms where the halogens are chlorine and/or bromine and A, B,C, D, E, are as above.

3. Polybromo dialkyl benzene of the general formula:

where R, and R are the same or different and are similar to R in (2).

4. Polybrominated phenols 0f the general formula:

where R and R are the same or different and can be H, alkyl preferablyof 1-5 carbon atoms, bromoalkyl, polybromoalkyl and the like; aryl,phenyl, bromoaryl, bromophenyl, polybromoaryl, polybromopenyl, NH NH Na,K, Li, Ca, Ba, Sb, Ti and the like;

O Ra.

5. Polybrominated biphenyls of the general formula:

where A to J are the same or different and can be H, Br, lower alkyl Cto C aryl,

O OHLX,

X being OH, NH,, ONH Na, K and the like.

6. Polybrominated terphenyls of the general formula:

B A N M L K D E F G H I where A to N are the same as in 5.

7. Polybrominated aniline of the general formula:

XNY

where A to E are the same as in 5, and X and Y are H, lower alkyl C to Caryl, bromoalkyl, polybromoalkyl, bromoaryl, polybromoaryl, phenylbromophenyl, polybromophenyl and the like.

8. Polybrominated aromatic mono and polyacids, anhydrides or esters ofthe same or the general formula:

9. Polybrominated bisphenol A of the general formula:

In the process of preparing the flame proofing agent of the presentinvention, there is also utilized a synergist which reacts with thehalobrominated organic material at the flame temperatures inducing itsdecomposition and liberating a nonflammable gas which forms a blanketaround the flaming substrate, displacing the oxygen from the vicinity ofthe same thus impeding the oxidation process of the combustion.

The synergists are normally metallic oxides of the general formula:

where Me can be Al, Ga, Si, Ge, As, Sb, Bi, Ti, Zr, and the like and nis the valence of the metal in its oxidized state. Especially are theoxides of aluminum, germanium, antimony and titanium useful.

These oxides must also be present in a fine particle state of the samesize as the halobrominated compound or smaller.

The synergist is blended with the halobrominated compound during thepreparation of the FR dispersion, the ratio of halobrominated compoundto synergist depending on the stability of the halobrominated materialand the reactivity of the particular metallic oxide employed. It wasfound that normally 3 to 7 parts halobrominated flame retarder for eachpart of metallic oxide, preferably 4-6 parts to 1 part, give the bestresults.

The emulsion polymers, commonly referred to as synthetic latices, arecommercially available materials, obtained by emulsion homoorco-polymerization of monomers of the general class:

where R and R can be the same or different and can be selected among1-1, Cl, Br, CH C H where n is 1 to 5 and m 2n 1, COOH, CONH CN, CH =CHC H and the like.

The preferred monomers are alkyl esters of acrylic and methacrylicacids, acryland methacryl amides, acrylonitrile, acrylic and methacrylicacids, maleic or fumaric acids and alkyl esters of the same vinyl andvinylidene chlorides, styrene and butadiene.

Due to the infinite number of possible combinations we will class thepolymers in the following group:

a. Acrylic latices, mainly homoor co-polymers of alkyl esters of acrylicor methacrylic acids which can also contain acrylic or methacrylic acid,acrylonitrile, acrylamide, n-methylol acrylamide, vinyl and vinylidienechlorides and the like. The alkyl group of the esters can also containhydroxyl groups. The presence of reactive groups, such as HO, CONH COOH,

suggests the possibility of further crosslinkage by the effect of heatleading to a higher molecular weight and thus much more stable polymers.These types of polymers are referred to as cross-linking, self-crosslinking 0r thermosetting latices.

b. Acrylonitrile Latices: where the major ingredient is acrylonitrilewhich can be found as homo polymers or copolymers as in (a).

. c. Vinylchloride Latices: where the major constituent is this monomerhomo-polymerized or copolymerized asin (a).

d. Vinylidine chloride latices;

e. ABS (acrylonitrile butadiene styrene) latices:

where these three monomers are the principal ingredients and can also becopolymerized with other monomers as in (a).

f. SBR (styrene butadiene rubber) latices.

g. Also there are employed emulsion polymers obtained by the reaction ofa polyisocyanate and an aliphatic polyol which can be a polyether, apolyester, or a polycaprolactone, the preferred polyisocyanate being amixture of isomers of toluene diisocyanate and the preferred polyolbeing a polyethylene glycol condensate having a molecular weight inexcess of 3,000, commonly referred to as a polyurethane latex.

The reason for blending these various monomers is to achieve polymerswith varying film properties, such as:

1. Feel or hand of film. This can vary from soft to hard and from tackyto dry. This parameter is measured by the glass transition temperature(T.G.) or in some cases by T (temperature at which the torsional modulusof an air dried film is 300 Kg/CM Both are measured in C and can rangefrom l00C to +100C. As a general rule, the lower the T6 or T the softerthe film, the film becoming harder with increasing temperatures.

2. Solvent swelling resistance. Latices are known to swell when wettedwith organic, especially chlorinated solvents, resulting in lack ofdurability to dry cleaning. This property is improved by introducingcross-linkable sites into the molecule of the polymer.

3. Film strength. The strength of the film is also improved byincreasaing the molecular weight of the polymer through the introductionof crosslinkable sites which are made to react by heat and/or catalysts.

4. Adhesion of film. This property is very important since thedurability of the flame retarder will greatly depend on it.

In the process of preparing the flame retardant dispersion 1 to 4 parts,preferably 2 to 3 parts, of a finely divided powdered halobrominatedorganic material is dispersed in 1 part of water containing 0.1 to 1% ofanionic wetting agent by the use of a high shear mixer. After additionis completed 0.1 to 1 part, preferably 0.2

to 0.4 part, based on the weight of the halobrominated.

organic compound of a metallic oxide is slowly added. After addition iscomplete the dispersion is stabilized by adding 0.1 to 0.5%, preferably0.2 to 0.3%, on the weight of the dispersion of a protective colloidsuch as ethoxy cellulose.

In the case when it is necessary to flame retard a given substrate 0.5to 1.5 parts, preferably 0.8 to 1.2 parts, of FR dispersion aredissolved in 1 part of water with mild agitation. To this solution 0.05to 0.4, preferably 0.1 to 0.3 part of a latex containing 35 topreferably 45 to 55%, of a polymer is added. In treating hydrophobicsubstrates, 0.5.to 1.5%, preferably 0.8 to 1.2% of a wetting agent isadded.

The'substrate to be treated is dipped in this solution and the excessremoved by squeezing between two rollers. The wet material is air driedin an oven at C to C, preferably 100C to 1 10C, and baked at C 9 to 18C,preferably 150C to 170C for /2 to minutes,

' preferably 1 /2 to3'minutes.

When the substrate to be treated is either intrinsically flame resistantor has been flamed retarded in a separate operation and must be treatedwith a flammable latex to achieve some desirable effect on the substratethe treating solution is prepared as follows: To 1 part of water 0.5 to1.5 parts, preferably 0.8 to 1.2 parts, of latex is added, and thesolution is mixed until uniform. 0.05 to 0.2 part, preferably 0.1 to0.15 part, based on the weight of the latex of FR dispersion is addedand mixed to uniformity. At this point any other needed auxiliaries,such as pigments, thickeners, fillers, plasticizers, wetting agents,catalysts, and the like, are incorporated in any required proportion andthe solution mixed.

The treating solution is now applied to the flame resistant substrate byany convenient way, such as padding, coating, printing, saturation andthe like and the wet goods are dried and baked as above.

EXAMPLE I 70 parts of finely divided decabromo biphenyl possessing anaverage particle size between 1 and 2 microns was slowly added to 50parts water containing 0.2% anionic wetting agent of the alkyl-arylsulfonate type, under strong agitation with a high speed, high shearmixer. After completing the addition of the brominated compound 12 partsof finely divided antimony-trioxide possessing an average particle sizebetween 1 and 2 microns were slowly added while agitation was continued.After all the antimony trioxide was added the resulting milky whitedispersion was stabilized by addition of 5 parts of a 4% aqueoussolution, having a viscosity of 300,000 centipoise, of ethoxycellulose.This dispersion, thus obtained, remained uniform after prolonged storageat room temperature and was designated dispersion I.

50 parts of dispersion I were now dissolved in 40 parts of water andparts of a 50% aqueous emulsion of a copolymer of ethyl acrylate andacrylamide having a T of -47C were added.

A woven fabric weighing 4 ozs. per square yard composed of 50% cotton50% polyester was now treated with this solution by immersing it in thesame and removing the excess by squeezing between two rollers. The wetpick-up was 90%. The fabric was now dried at 1 10C and baked at 150C for3 minutes.

The fabric thus obtained was quite soft to the feel was further softenedby padding it through a 10% emulsion of polyethylene softener in water.

The flame resistance of the fabric thus treated was evaluated by testingaccording to test method given in Standard for the Flammability ofChildrens Sleepwear" DOC FF3-71 giving an initial average char length of1 V2 inches and 2 inches after 50 launderings and tumble dryings.

EXAMPLE [1 70 parts of finely divided hexabromo benzene having anaverage particle size between 1 and 2 microns were dispersed in 50 partsof water in a similar fashion to dispersion l. parts of aluminum oxidewere added to the dispersed brominated compound and this dispersion wasstabilized as dispersion I. This material was designated dispersion ll.

40 parts of dispersion 11 were dissolved in 52 parts of water and 8parts of a 50% emulsion of a styrene butadiene copolymer having a glasstransition temperature of C were added.

A piece of cotton circular knit weighing 8 02s- /yd was immersed in thissolution and the excess removed by squeezing between two rollers. Thewet pickup was and the fabric was dried at 110C and baked at C for 3minutes. The fabric was softened by padding through a 10% emulsion of apolyethylene softener and dried.

The fabric was judged flame retardant by using method outlined in DDCFF3-7 l giving an initial average char length of 1 inch and 2 /2 inchesafter 50 launderings and tumble dryings.

EXAMPLE III 70 parts of finely divided pentabromo toluene and 20 partsof titanium dioxide having an average particle size of between 1 and 2microns were dispersed in 50 parts of water as in Example I. Thisdispersion was designated dispersion Ill.

50 parts of dispersion III were dissolved in 40 parts of water and 10parts of a 50% acrylonitrile-styrenebutadiene latex having a glasstransition temperature of 60C were added to this solution. The resultingmixture was padded onto a woven fabric composed of 80% rayon and 20%cellulose diacetate in a similar fashion as in Examples I and II. Thefabric was dried at 1 10C, baked at 150C, top softened with a 10%emulsion of a polyethylene softener and redried.

The treated fabric gave an average char length of 3 inches initially,when treated according to AATCC Flammability Test 34-1967, an averagechar length of 4 inches after 5 launderings and tumble dryings and anaverage char length of 5 inches after 5 commercial dry cleanings.

EXAMPLE IV 70 parts of Tris dibromophenyl phosphate and 10 parts ofantimony trioxide having an average particle size between 1 and 2microns were dispersed in 40 parts of water as in Example 1. Thisdispersion was designated dispersion IV.

50 parts of a 50% emulsion of a butyl acrylate N methylol acrylamideacrylonitrile copolymer latex having a glass transition temperature of0C were dispersed in 30 parts of water. To this solution 10 parts of a50% aqueous dispersion of disperse blue 1 (color index No. 42025) and 10parts of dispersion IV were added and the resulting mixture agitateduntil uniform.

A 100% woven fiberglass drapery fabric was immersed in this solution,the excess removed by squeezing between two rollers to obtain a wetpick-up of 50%, dried at 1 10C and baked at 150C for 3 minutes.

This fabric gave an average char length of 3 inches when tested usingAATCC flammability test 34-1967 initially, after 5 launderings andtumble drying and 5 commercial dry cleanings.

EXAMPLE V 70 parts of finely divided tribromoaniline and 15 parts ofmicropulverized aluminum trioxide having a particle size of between 1and 2 microns were dispersed in 50 parts of water following proceduregiven in Example I. This dispersion was designated as dispersion V.

0.5 parts of tetrasodium pyrophosphate were dissolved in 14.5 parts ofwater. Under strong agitation 10 parts of a finely divided clay andparts of dispersion V were added. Upon completion of the addition 45parts of a 50% aqueous emulsion of a polymer obtained by thecopolymerization of ethyl acrylate, n-methylol acrylamide, acrylonitrileand acrylic acid having a glass transition temperature of 2C. were mixedin. The viscosity of this dispersion was adjusted to 35,000 centipoisesby adding 24 parts of a 4% solution of methoxy cellulose. Finally, 1part of a solution of oxalic acid (acid catalyst) were mixed into thisdispersion. This dispersion was designated V-A.

A piece of the 80% rayon 20% cellulose diacetate fabric treated inExample III was coated on one side with dispersion V-A using a doctorblade to a loading of 70% on the weight of the fiber. The fabric wasdried at 125C and cured at 160C for 2 minutes.

The fabric thus treated gave a char length of 3 inches when testedaccording to AATCC method 34-1967, initially after 5 launderings and 5dry cleanings. The same fabric coated with the same composition, butwithout dispersion V was consumed entirely when tested by thisflammability method.

EXAMPLE VI Parts By Weight Vl-A Vl-B Water 300 300 Anionic DispersingAgent l l Hydroxyethyl Cellulose Thickener 5 5 Talc I25 125 RutileTitanium Dioxide 225 225 50% Solids Vinylacetateethylacrylute copolymer400 400 Dispersion VI 45 The dispersion were prepared by predissolvingthe ingredients in the given order in a tank equipped with a high-speedhigh-shear mixer and then transferring the resulting dispersion into thepebble mill and milling for 5 hours.

Two pieces of plywood were coated on both sides with dispersions VI-Aand Vl-B using a paint brush and air dried at room temperature.

The flammability of both pieces of plywood was tested by applying tothem a flame from a butane blow torch for seconds. The piece of plywoodtreated with dispersion VI-A immediately extinguished after removal ofthe blow torch giving a charred surface where the flame was in contactwith the coating, whereas the plywood coated with dispersion VI-Bcontinued burning until completely consumed.

EXAMPLE VII 70 parts of finely dividedhexachlorocyclopentadienodibromocyclooctane and 10 parts ofmicropulverized antimony trioxide having a particle size between 1 and 2microns were dispersed in 40 parts of water following procedure given inExample I. This dispersion was designated dispersion Ill.

parts of dispersion Vll were dispersed in 40 parts of water and 40 partsof a 50% aqueous emulsion of a 5 polymer obtained by reaction of amixture of isomers of toluene diisocyanate and a condensation product ofethylene glycol having a molecular weight of approximately 4,000.

A piece of 100% nylon upholstery fabric was immersed in this solutionand excess removed by squeezing between two rollers to achieve a 70% wetpickup and then dried at 125C.

The fabric thus treated was judged flame retardant when it gave a 3inches char length when listed according to AATCC method 34-1969,whereas the untreated fabric burned the entire length when testedaccording to the same method.

Using and techniques and formulations of any of the examples given,namely, 1 through 7, the following compounds may be used for applicationto the various bases identified in the several examples:

pentabromo phenol tribromo aniline dibromo benzoic acid Polybrominatedphenol Polybrominated aniline Polybrominated benzoic acid Trisphosphates of polybrominated phenols Polybrominated cyclopentanePolybrominated cyclohexane Polybrominated cyclooctane Polybrominatedcyclodecane Polybrominated cyclododecaneHexachlorocyclopentadienodibromocyclooctaneN,N'-ethyl-bis(dibromonorbornene-dicarboximide) Per chloro pentacyclodecane Polybrominated biphenyl hexabromo Polybrominated biphenyloxide decabromo biphenoloxide Polybrominated benzene hexabromoPolybrominated toluene pentabromo toluene Polybrominated chlorotoluenetetrabromo tetrabromo cyclo hexabromo cyclo hexabromo cyclo hexabromocyclo hexabromo cyclo hexabromo cyclo reduced to an average particlesize below 2 microns, and being in weight ratio of 1:4 parts ofbrominated compound to 0. 1:1 part of metallic oxide,

said high molecular weight polymeric binder being present in amountsufficient to secure said brominated organic compound and metallic oxideflame retardant composition to said material, and drying and curing saidtreated material, wherein the total amount of flame retardant depositedon said material is effective to reduce the flammability of the textileand is durable to laundering and dry clean- 2. The method in accordancewith claim 1 whereby drying is carried out at elevated temperatures of100l75C.

3. The method in accordance with claim 1 in which the flame retardant isapplied by'padding.

substantially totally insoluble in water, having been.

4. The method in accordance with claim 1 in which the flame retardant isapplied by knife coating.

5. The method of claim 1 wherein the brominated solid organic materialis selected from the group consisting of:

Polybrominated biphenyl Polybrominated biphenyl oxide Polybrominatedbenzene Polybrominated toluene Polybrominated chlorotoluenePolybrominated phenol Polybrominated aniline Polybrominated benzoic acidTris phosphates of polybrominated phenols Polybrominated cyclopentanePolybrominated cyclohexane Polybrominated cyclooctane Polybrominatedcyclodecane Polybrominated cyclododecaneHexachlorocyclopentadieno-dibromocyclooctan and N,N -ethyl-bis(dibromo-norbornenedicarboximide Y 6. The method of claim 1 wherein themetallic oxide is selected from the group consisting of: Al, Ga, Si, Ge,As, Sb, Bi, Ti and Zr oxides.

7. The method of claim 1 wherein the latexes are selected from the groupconsisting of:

Polymers of esters of acrylic acid Styrene butadiene copolymersAcrylonitrile-styrene-butadiene copolymers Copolymers of ethylacrylic-N-methylol acrylamideacrylonitrile-acrylic acid Vinylacetate-ethyl acrylate copolymers Butyl acrylate-Nmethylolacrylamideacr'ylonitrile,

and

Polyurethane polymers.

8. A textile material inherently flammable, rendered and, N,N -ethyl-bis(dibromo-norbornenedicarboximide the metallic oxide is selected from thegroup consisting of:

Al, Ga, Si, Ge, Sb, Bi, Ti, and Zr oxides,

and

the latex is selected from the group consisting of:

polymers of esters of acrylic acid styrene butadiene copolymersacrylonitrile-styrene-butadiene copolymers copolymers of ethylacrylate-N-methylol acrylamideacrylonitrile-acrylic acid vinylacetate-ethyl acrylate copolymers butyl acrylate-N-methylolacrylamide-acrylonitrile and polyurethane polymers.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No-3,877,974 I D t April 15L 1975 1nventor(s) Vladimir Mischutin It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the Title Page, "[21] Appl. No. 330,731"

should read: [21] Appl. No. 300,731

Signed and sealed this 17th day of June 1975.

1 Arrest:

C. MARSHALL DAMN T791? 3. I"--;i3i-Z Co missi oner of Patents .tte tinGfficer and Trademarks F ORM PO-1050 (10-69) USCOMMDC 60376-P89 w u.s.covenant"? PRINTING OFFICE Isis o-assqn.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3877,974 Dated April 1.5 1975 Inventor(s) Vladimir Mischutin It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the Title Page, "[21] Appl. No. 330,731"

.Signcci and sealer. this 17th day of June 1975.

C. ZZARSHALL DANE-3 Coflmissi oner of fate-tits and Trademarks.ktterttng C'fficer FORM PO-1050 (10-69) USCOMM-DC 60376-P69 i ".5.GOVERNMENT PRINTING OFFICE I9, 0-$5G'l34,

1. A METHOD OF RENDERING FLAMMABLE TEXTILE MATERIALS FLAME RETARDANTWHICH COMPRISES: TREATING SAID MATERIALS WITH A FLAME RETARDANTCOMPOSITION CONSISTING ESSENTIALLY OF ABROMINATED, ORGAIC AROMATIC ORCYCLIC COMPOUND AD A METALLIC OXIDE, IN AQUEOUS DISPERSION, IN ADMIXTUREWITH AN AQUEOUS EMULSION OF A SUITALEE HIGH MOLECULAR WEIGHT POLYMERICADHESIVE BIN BINDER, SAID BROMINATED COMPOUND AND SAID METALLIC OXIDEBEING SOLIDS AT ROOM TEMPERATURE, SUBSTANTIALLY TOTALLY INSOLUBLE INWATER, HAVING BEEN REDUCED TO AN AVERAGE PARTICLE SIZE BELOW 2 MICRONS,AND BEING IN WEIGHT RATIO OF 1:4 PARTS OF BROMINATED COMPOUND OF 0.1:1PART OF METALLIC OXIDE, SAID HIGH MOLECULAR WEIGHT POLYMERIC BINDERBEING PRESENT IN AMOUNT SUFFICIENT TO SECURE SAID BROMINATED ORGANICCOMPOUND AND METALLIC OXIDE FLAME RETARDANT COMPOSITION TO SAIDMATERIAL, AND DRYING AND CURING SAID TREATED MATERIAL, WHEREIN THE TOTALAMOUNT OF FLAME RETARDANT DEPOSITED ON SAID MATERIAL IS EFFECTIVE TOREDUCE THE FLAMMABILITY OF THE TEXTILE AND IS DURABLE TO LAUNDERING ANDDRY CLEANING.
 2. The method in accordance with claim 1 whereby drying iscarried out at elevated temperatures of 100*-175*C.
 3. The method inaccordance with claim 1 in which the flame retardant is applied bypadding.
 4. The method in accordance with claim 1 in which the flameretardant is applied by knife coating.
 5. The method of claim 1 whereinthe brominated solid organic material is selected from the groupconsisting of: Polybrominated biphenyl Polybrominated biphenyl oxidePolybrominated benzene Polybrominated toluene Polybrominatedchlorotoluene Polybrominated phenol Polybrominated anilinePolybrominated benzoic acid Tris phosphates of polybrominated phenolsPolybrominated cyclopentane Polybrominated cyclohexane Polybrominatedcyclooctane Polybrominated cyclodecane Polybrominated cyclododecaneHexachlorocyclopentadieno-dibromocyclooctane and N,N'' -ethyl-bis(dibromo-norbornene-dicarboximide).
 6. The method of claim 1 wherein themetallic oxide is selected from the group consisting of: Al, Ga, Si, Ge,As, Sb, Bi, Ti and Zr oxides.
 7. The method of claim 1 wherein thelatexes are selected from the group consisting of: Polymers of esters ofacrylic acid Styrene butadiene copolymersAcrylonitrile-styrene-butadiene copolymers Copolymers of ethylacrylic-N-methylol acrylamideacrylonitrile-acrylic acid Vinylacetate-ethyl acrylate copolymers Butyl acrylate-N-methylolacrylamide-acrylonitrile, and Polyurethane polymers.
 8. A textilematerial inherently flammable, rendered flame resistant by theimpregnation with a flame retardant composition in accordance with theprocess of claim
 1. 9. The method of claim 1 wherein the brominatedcompound is selected from the group consisting of: Polybrominatedbiphenyl Polybrominated biphenyl oxide Polybrominated benzenePolybrominated toluene Polybrominated chlorotoluene Polybrominatedphenol Polybrominated aniline Polybrominated benzoic acid Trisphosphates of polybrominated phenols Polybrominated cyclopentanePolybrominated cyclohexane Polybrominated cyclooctane Polybrominatedcyclodecane Polybrominated cyclododecaneHexachlorocyclopentadieno-dibromocyclooctane, and, N,N'' -ethyl-bis(dibromo-norbornene-dicarboximide), the metallic oxide is selected fromthe group consisting of: Al, Ga, Si, Ge, Sb, Bi, Ti, and Zr oxides, andthe latex is selected from the group consisting of: polymers of estersof acrylic acid styrene butadiene copolymersacrylonitrile-styrene-butadiene copolymers copolymers of ethylacrylate-N-methylol acrylamide-acrylonitrile-acrylic acid vinylacetate-ethyl acryLate copolymers butyl acrylate-N-methylolacrylamide-acrylonitrile and polyurethane polymers.